CN102247853B - Catalyst for preparing gamma-butyrolactone through maleic anhydride normal-pressure gas-phase hydrogenation - Google Patents
Catalyst for preparing gamma-butyrolactone through maleic anhydride normal-pressure gas-phase hydrogenation Download PDFInfo
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Abstract
The invention relates to the field of catalyst containing metal, or metal oxide, or metal hydroxide, and specifically relates to a catalyst for preparing gamma-butyrolactone through maleic anhydride normal-pressure gas-phase hydrogenation. The catalyst is composed of 0 to 49 w% of CuO, 10 to 50 w% of ZnO, and 22 to 79 w% of Al2O3-TiO2-active carbon blend. The Al2O3-TiO2-active carbon blend is composed of 21 to 80 w% of Al2O3, 10 to 50 w% of TiO2 and 10 to 49 w% of active carbon. According to the invention, toxic component Cr element is not contained in the catalyst. Therefore, the catalyst belongs to green catalysts. The catalyst is used under a high maleic anhydride liquid hour space velocity, and has high maleic anhydride conversion rate, which is 100%, and high gamma-butyrolactone selectivity, which is above 98%. The activity of the catalyst can maintain stabile for a long time, which is more than 1800 hours. Therefore, the catalyst is a catalyst with a relatively high cost performance for preparing gamma-butyrolactone through maleic anhydride normal-pressure gas-phase hydrogenation.
Description
Technical field
The present invention relates to comprise the catalyst of copper, zinc, aluminium and titanium, be specifically related to comprise the catalyst of copper, zinc, aluminium and titanyl compound.
Background technology
Gamma-butyrolacton is called 1 again, and the 4-butyrolactone is a kind of important fine chemical product, can be used as Ciprofloxacin, piracetam, Cobastab
1, PVP etc. raw materials for production, wherein pyrrolidones can be used to produce the adhesive of latex in nylon monomer, plasticizer, the floor wax, the NMF of cosmetics etc.Gamma-butyrolacton conducts electricity very well because boiling point is high, and stability is high, and safe in utilization using always made high boiling solvent, extractant and absorbent, and the special solvent that also can be used as high conductivity is used for the electrolyte of lithium battery and electrical equipment.Gamma-butyrolacton has wide practical use in industrial circles such as petrochemical industry, weaving, spices, agricultural chemicals and medicine.
The suitability for industrialized production gamma-butyrolacton mainly contains four kinds of process routes: be the Reppe method of raw material with acetylene and formaldehyde; With the butadiene is the acetoxylation method of raw material; With agricultural byproducts is the furfural hydrogenation method of raw material; With the cis-butenedioic anhydride is the maleic anhydride hydrogenation method of raw material.
Recent two decades comes, and n butane oxidation prepares cis-butenedioic anhydride large-scale industrial production; And in recent years, the employing of large-scale fluidized bed and mobile oxidation technology declines to a great extent the cis-butenedioic anhydride production cost.Therefore, the cis-anhydride normal pressure gas phase hydrogenation prepares gamma-butyrolacton technology and more and more has competitiveness.
The catalyst of maleic anhydride hydrogenation system gamma-butyrolacton employing at present roughly can be divided three classes: noble metal catalyst, Ni series catalysts and Cu series catalysts, wherein the Cu-Zn series catalysts is the domestic and international research focus.
Chinese patent CN1058400A discloses a kind of by Cu, ZnO, Al
2O
3, reaching at least a catalyst that mixes in Ni, Ru, Ce, four kinds of elements of Zr, the cis-butenedioic anhydride conversion per pass is near 100%, and the selectivity of gamma-butyrolacton and oxolane reaches 95%.
Chinese patent CN1111167A discloses a kind of by CuO, ZnO, Al
2O
3Catalyst with the 4th component Pd or Pt composition.With CuO, ZnO and Al
2O
3Be parent, the 4th component is sprayed on the parent surface.The cis-butenedioic anhydride conversion ratio is 100%, and the gamma-butyrolacton selectivity is 92.7%.
Chinese patent CN1139106A discloses a kind of by CuO, ZnO, Cr
2O
3, ZrO
2The catalyst of forming.This method can obtain near the gamma-butyrolacton selectivity more than 100% the cis-butenedioic anhydride conversion ratio and 85% under high-speed.
Chinese patent CN1298759A discloses a kind of by CuO, ZnO, Al
2O
3, auxiliary agent (BaO or Pd).The cis-butenedioic anhydride conversion per pass is 100%, and the gamma-butyrolacton selectivity can reach 93～98%.
U.S. Pat 5122495 discloses a kind of CuO, ZnO, Al
2O
3Catalyst.The 400g catalyst of in reactor, packing into, under hydrogen acid anhydride mol ratio 230～280 conditions, the cis-butenedioic anhydride conversion ratio is about 100%, the selectivity of gamma-butyrolacton about 85～95%.But catalyst can only use 100～500h continuously, just needs regeneration under 400～450 ℃ of high temperature, thereby has increased the difficulty of commercial Application.
Though above-mentioned existing patented technology respectively has its characteristics, its weak point is also respectively arranged, for example: reaction temperature is higher, the raw material air speed is lower, the gamma-butyrolacton selectivity is not high, catalyst activity is unstable, one way weak point in service life etc.Therefore, develop the catalyst that the cis-anhydride normal pressure hydrogenation preparing gama-butalactone of have greater activity (particularly low temperature active), high selectivity and stability uses and have realistic meaning.
Summary of the invention
The technical problem that will solve of the present invention provides the cis-anhydride normal pressure gas phase hydrogenation and prepares the Catalysts and its preparation method that gamma-butyrolacton is used.This catalyst is a green catalyst, does not contain poisonous component Cr element, has the advantage of high activity and high selectivity.
The technical scheme that the present invention solves the problems of the technologies described above is:
A kind of cis-anhydride normal pressure gas phase hydrogenation prepares the catalyst that gamma-butyrolacton is used, and this catalyst is by 10～49w%CuO, 10～50w%ZnO and 22～79w%Al
2O
3-TiO
2-active carbon blend is formed, wherein Al
2O
3-TiO
2-active carbon blend is by 21～80w%Al
2O
3, 10～50w%TiO
2Form with 10～49w% active carbon, and prepare by following method:
(1) with Cu (NO
3)
23H
2O and Zn (NO
3)
29H
2O is dissolved in the deionized water, adds Al
2O
3-TiO
2-active carbon blend, 70 ℃ were stirred 1 hour down, wherein Cu (NO
3)
23H
2O, Zn (NO
3)
29H
2O and Al
2O
3-TiO
2The weight ratio of-active carbon blend is Cu (NO
3)
23H
2O: Zn (NO
3)
26H
2O: Al
2O
3-TiO
2-active carbon blend=13～61: 16～76: 9～32;
(2) under 60～80 ℃, slowly add the precipitating reagent aqueous solution of 0.1～1mol/L, mix, be that 6～8 depositions finish up to the pH of system value, wherein said precipitating reagent is Na
2CO
3, NaHCO
3, NaOH, K
2CO
3, KHCO
3, KOH, NH
4HCO
3In one or more;
(3) the deposition ageing is 12 hours, filters, washs; 120 ℃ dry 12 hours down, 450 ℃ of following roastings 3 hours obtain described catalyst;
Wherein, described Al
2O
3-TiO
2-active carbon blend is prepared by following method:
With TiCl
4With the watery hydrochloric acid dilution, add Al (NO
3)
39H
2O and 100～200 purpose active carbon powders, 70 ℃ were stirred 1 hour down, wherein TiCl
4, Al (NO
3)
39H
2O and 100～200 purpose active carbon weight ratios are TiCl
4: Al (NO
3)
39H
2O: 100～200 purpose active carbon=10.1～42.5: 33～121.3: 4.7～20.1; Under 70 ℃, add the Na of 0.5mol/L
2CO
3The aqueous solution mixes, and is that 6～8 depositions finish up to the pH of system value; Deposition ageing 12 hours is filtered, is washed, and drying is 12 hours under 130 ℃, grinds to form 100～200 purpose powder, 800 ℃ of following calcinations 3 hours, obtains described Al
2O
3-TiO
2-active carbon blend.
Cis-anhydride normal pressure gas phase hydrogenation of the present invention prepares the catalyst that gamma-butyrolacton is used, and this catalyst is by 20～45w%CuO, 20～40w%ZnO and 40～60w%Al
2O
3-TiO
2-active carbon blend is formed.
Catalyst of the present invention, employed precipitating reagent better is Na in its preparation method
2CO
3
Catalyst of the present invention, wherein said Al
2O
3-TiO
2-active carbon blend is preferably by 40～60w%Al
2O
3, 20～40w%TiO
2Form with 20～40w% active carbon.
Active carbon of the present invention is this area active carbon commonly used.Active carbon of the present invention can be untreated active carbon, can also be treated active carbon, and wherein the latter can be prepared by following method: with 100～200 purpose activated carbon powders; Put into deionized water; Stir heating down, seethed with excitement 2 hours, cooled and filtered is dry.
When catalyst of the present invention carries out catalytic hydrogenation to cis-butenedioic anhydride, adopt the method for this area Fixed Bed Gas Phase hydrogenation commonly used, its reaction condition is: 270 ℃ of reaction temperatures, reaction pressure 0.15MPa, cis-butenedioic anhydride liquid air speed 0.15h
-1, hydrogen acid anhydride mol ratio 50: 1.
Catalyst according to the invention must carry out reduction activation before use.Activation condition is: the hydrogen (nitrogen hydrogen mol ratio is 9: 1) with nitrogen dilution carries out activation to catalyst, under 0.2MPa pressure, catalyst is carried out activation under 300 ℃, till the reactor outlet end does not have the globule.
Catalyst of the present invention has the following advantages: 1. catalyst is by activated centre Cu, auxiliary agent ZnO, carrier A Al
2O
3-TiO
2-active carbon blend is formed, and does not contain poisonous component Cr element, is green catalyst.2. catalyst has high activity and high selectivity, and wherein the cis-butenedioic anhydride conversion ratio reaches 100%, and the gamma-butyrolacton selectivity is greater than 98%, and the catalytic activity time reached more than 1800 hours.3. catalyst can use under high cis-butenedioic anhydride liquid hourly space velocity (LHSV), and cis-butenedioic anhydride liquid air speed reaches 0.1～0.3h
-1, hydrogen acid anhydride mol ratio 20: 1～200: 1.
The specific embodiment
Embodiment 1:
1. Preparation of catalysts
1.1. preparation Al
2O
3-TiO
2-active carbon blend
1.1.1.Al
2O
3-TiO
2The preparation of-active carbon blend
With 14.50g TiCl
4(8.5mL) hydrochloric acid with 1.0125mol/L is diluted to 1000mL, adds 37.50g Al (NO
3)
39H
2Pretreated 100～200 purpose active carbons of O and 4.20g, 70 ℃ were stirred 1 hour down; Under 70 ℃, slowly add the Na of 0.5mol/L then
2CO
3The aqueous solution mixes, and is that 7.4 depositions finish up to the pH value; Precipitated ageing again 12 hours, and filtered, washing, 130 ℃ dry 12 hours down, grind to form 100～200 purpose powder, 500 ℃ of following roastings 3 hours make Al
2O
3-TiO
2-active carbon blend 20.03g.Wherein active carbon carries out preliminary treatment through following method: with 100～200 purpose active carbons, place the deionized water beaker is housed, stir heating down, seethed with excitement 2 hours, the cooled and filtered drying obtains.
1.1.2.Al
2O
3-TiO
2The composition of-active carbon blend
Adopt XPS analysis Al
2O
3-TiO
2-active carbon blends surface atom valence state, and with the method for ICP-AES to Al
2O
3-TiO
2Each component of-active carbon blend is carried out the branch detection by quantitative, and analytical method is following:
Adopting the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, is excitaton source with Al K α, and the resolution ratio of instrument is 1.15eV, is fixed in the sample holder XPS of test sample article behind the sample compressing tablet.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company that each constituent content is analyzed.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, secondary air amount 1.0L/min, atomization gas flow 0.8L/min.
Analysis result shows Al
2O
3-TiO
2-active carbon blend consists of Al
2O
350w%, TiO
230w%, carbon 20w%.
1.2. preparation catalyst
1.2.1. Preparation of catalysts
1.2.1.1. with 18.50g CuNO
33H
2O and 22.40g Zn (NO
3)
26H
2O is dissolved in the 1000mL deionized water, adds 8.25gAl
2O
3-TiO
2-active carbon blend (the Al for preparing in advance by step 1.1.
2O
3-TiO
2-active carbon blend), 70 ℃ were stirred 1 hour down.
1.2.1.2.70 under ℃, slowly add the Na of 0.5mol/L
2CO
3The aqueous solution mixes, and is that 7 depositions finish up to the pH of system value.
1.2.1.3. deposition ageing 12 hours is filtered, washing, 120 ℃ dry 12 hours down, 450 ℃ of following roastings 3 hours obtain catalyst finished product 19.98g.
1.2.2. the composition of catalyst
Adopt XPS analysis catalyst surface atom valence state, and with the method for ICP-AES each component of catalyst is carried out the branch quantitative analysis, analytical method is following:
Adopting the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, is excitaton source with Al K α, and the resolution ratio of instrument is 1.15eV, is fixed in behind the sample compressing tablet in the sample holder and detects.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company that each constituent content is analyzed.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, secondary air amount 1.0L/min, atomization gas flow 0.8L/min.
Analysis result shows that this catalyst comprises the ZnO of the CuO of 30w%, 30w%, the Al of 20w%
2O
3, 12w% TiO
2, 8w% carbon.
Catalyst consists of the CuO of 30w%, the ZnO of 30w% and the Al of 40w%
2O
3-TiO
2-active carbon blend, wherein Al
2O
3-TiO
2-active carbon blend consists of Al
2O
350w%, TiO
230w%, carbon 20w%.
2. cis-butenedioic anhydride catalytic hydrogenation reaction
2.1. the catalyst granules that makes in the step 1 is inserted in the fixed bed reactors of Φ 14mm, packed height is 5cm.H with 10%
2/ N
2Mist carries out activation to catalyst under 0.2MPa, 280 ℃, till the reactor outlet end does not have the globule.
2.2. at 270 ℃, under the normal pressure, cis-butenedioic anhydride liquid air speed 0.15h
-1, under 50: 1 the condition of hydrogen acid anhydride mol ratio catalyst is estimated.Product is collected in the ice-water bath cooling, adopts gas chromatographic analysis, cis-butenedioic anhydride conversion ratio 100%, and the gamma-butyrolacton selectivity is greater than 98%, and catalyst used 2000 hours continuously, and active and selectivity does not obviously reduce.
Embodiment 2:
1. Preparation of catalysts
1.1. preparation Al
2O
3-TiO
2-active carbon blend
1.1.1.Al
2O
3-TiO
2The preparation of-active carbon blend
With 13.62gTiCl
4(7.9mL) hydrochloric acid with 1.0125mol/L is diluted to 800mL, adds 30.08Al (NO
3)
39H
2O and 6.73g100～200 purpose active carbons stirred 1 hour down in 70 ℃; Under 70 ℃, slowly add the Na of 0.5mol/L then
2CO
3The aqueous solution mixes, and is that 7 depositions finish until the pH of system value; Precipitated ageing again 12 hours, and filtered, washing, 130 ℃ dry 12 hours down, grind to form 100～200 purpose powder, 500 ℃ of following roastings 3 hours make Al
2O
3-TiO
2-active carbon blend 20.01g.
1.1.2.Al
2O
3-TiO
2The composition of-active carbon blend
Adopt XPS analysis Al
2O
3-TiO
2-active carbon blends surface atom valence state, and with the method for ICP-AES to Al
2O
3-TiO
2Each component of-active carbon blend is carried out the branch detection by quantitative, and analytical method is following:
Adopting the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, is excitaton source with Al K α, and the resolution ratio of instrument is 1.15eV, is fixed in behind the sample compressing tablet in the sample holder and detects.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company that each constituent content is analyzed.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, secondary air amount 1.0L/min, atomization gas flow 0.8L/min.
Analysis result shows Al
2O
3-TiO
2-active carbon blend consists of Al
2O
340w%, TiO
228w%, carbon 32w%.
1.2. preparation catalyst
1.2.1. Preparation of catalysts
With 13.66g CuNO
33H
2O and 28.34g Zn (NO
3)
26H
2O is dissolved in the 1000mL deionized water, adds the Al that makes among the 8.35g step 1.1.
2O
3-TiO
2-active carbon blend, 70 ℃ were stirred 1 hour down.Under 75 ℃, slowly add the Na of 0.5mol/L again
2CO
3The aqueous solution mixes, and is 7.5 o'clock up to the pH of system value, and deposition finishes; And then deposition ageing 12 hours, filter, washing, 120 ℃ dry 12 hours down, 450 ℃ of following roastings 3 hours obtain catalyst finished product 19.98g.
1.2.2. the composition of catalyst
Adopt XPS analysis catalyst surface atom valence state, and with the method for ICP-AES each component of catalyst is carried out the branch quantitative analysis, analytical method is following:
Adopting the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, is excitaton source with Al K α, and the resolution ratio of instrument is 1.15eV, is fixed in behind the sample compressing tablet in the sample holder and tests.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company that each constituent content is analyzed.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, secondary air amount 1.0L/min, atomization gas flow 0.8L/min.
Analysis result shows that this catalyst comprises the ZnO of the CuO of 22w%, 37.5w%, the Al of 16.2w%
2O
3, 11.3w% TiO
2, 13w% carbon.
Catalyst consists of the CuO of 22w%, the ZnO of 37.5w% and the Al of 40.5w%
2O
3-TiO
2-active carbon blend, wherein Al
2O
3-TiO
2-active carbon blend consists of Al
2O
340w%, TiO
228w%, carbon 32w%.
2. cis-butenedioic anhydride catalytic hydrogenation reaction
2.1. above-mentioned catalyst finished product is broken, to choose 20～40 order catalyst granules and insert in the fixed bed reactors of Φ 14mm, packed height is 5cm.Adopt the method in the instance 1 that catalyst is carried out reduction activation.
2.2. under normal pressure, 270 ℃ of reaction temperatures, cis-butenedioic anhydride liquid air speed 0.15h
-1, catalyst is estimated under 50: 1 the condition of hydrogen acid anhydride mol ratio.Adopt gas chromatographic analysis, cis-butenedioic anhydride conversion ratio 100%, the gamma-butyrolacton selectivity was used 2000 hours greater than 95% continuously, and catalyst activity does not have significant change.
Embodiment 3:
1. Preparation of catalysts
1.1. preparation Al
2O
3-TiO
2-active carbon blend
1.1.1.Al
2O
3-TiO
2The preparation of-active carbon blend
With 18.59gTiCl
4(10.8mL) hydrochloric acid with 1.0125mol/L is diluted to 1000mL, adds 32.85g Al (NO
3)
39H
2Pretreated 100～200 purpose active carbons of O and 4.52g, 70 ℃ were stirred 1 hour down; Under 70 ℃, slowly add the Na of 0.5mol/L again
2CO
3The aqueous solution mixes, and is that 7.5 depositions finish up to the pH value; Precipitated ageing again 12 hours, and filtered, washing, 130 ℃ dry 12 hours down, grind to form 100～200 purpose powder, 500 ℃ of following roastings 3 hours make Al
2O
3-TiO
2-active carbon blend 20.15g.
Wherein active carbon carries out preliminary treatment through following method: with 100～200 purpose active carbons, place the deionized water beaker is housed, stir heating down, seethed with excitement 2 hours, the cooled and filtered drying obtains.
1.1.2.Al
2O
3-TiO
2The composition of-active carbon blend
Adopt XPS analysis Al
2O
3-TiO
2-active carbon blends surface atom valence state, and with the method for ICP-AES to Al
2O
3-TiO
2Each component of-active carbon blend is carried out the branch detection by quantitative, and analytical method is following:
Adopting the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, is excitaton source with Al K α, and the resolution ratio of instrument is 1.15eV, is fixed in the sample holder vacuum detecting behind the sample compressing tablet.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company that each constituent content is analyzed.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, secondary air amount 1.0L/min, atomization gas flow 0.8L/min.
Analysis result shows Al
2O
3-TiO
2-active carbon blend consists of Al
2O
342w%, TiO
237w%, carbon 21w%.
1.2. preparation catalyst
1.2.1. Preparation of catalysts
With 14.30g CuNO
33H
2O and 15.67gZn (NO
3)
26H
2O is dissolved in the 1000mL deionized water, adds the Al that 12.04g step 1.1. obtains
2O
3-TiO
2-active carbon blend, 70 ℃ were stirred 1 hour down.Under 70 ℃, slowly add the Na of 0.5mol/L
2CO
3The aqueous solution mixes, and is that 6.5 depositions finish up to the pH of system value.Precipitated ageing again 12 hours, and filtered, washing, 120 ℃ dry 12 hours down, 450 ℃ of following roastings 3 hours obtain catalyst finished product 20.64g.
1.2.2. the composition of catalyst
Adopt XPS analysis catalyst surface atom valence state, and with the method for ICP-AES each component of catalyst is carried out the branch quantitative analysis, analytical method is following:
Adopting the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, is excitaton source with Al K α, and the resolution ratio of instrument is 1.15eV, is fixed in behind the sample compressing tablet in the sample holder and detects.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company that each constituent content is analyzed.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, secondary air amount 1.0L/min, atomization gas flow 0.8L/min.
The result shows that this catalyst comprises the ZnO of the CuO of 22w%, 20w%, the Al of 24.3w%
2O
3, 21.5w% TiO
2, 12.2w% carbon.
Catalyst consists of the CuO of 22w%, the ZnO of 20w% and the Al of 58w%
2O
3-TiO
2-active carbon blend, wherein Al
2O
3-TiO
2-active carbon blend consists of Al
2O
342w%, TiO
237w%, carbon 21w%.
2. cis-butenedioic anhydride catalytic hydrogenation reaction
2.1 the catalyst granules that obtains in the step 1 is inserted in the fixed bed reactors of Φ 14mm, packed height is 5cm.H with 10%
2/ N
2Mist carries out activation to catalyst under 0.2MPa, 280 ℃, till the reactor outlet end does not have the globule.
2.2 at 270 ℃, under the normal pressure, cis-butenedioic anhydride liquid air speed 0.15h
-1, under 50: 1 the condition of hydrogen acid anhydride mol ratio catalyst is estimated.Adopt gas chromatographic analysis, cis-butenedioic anhydride conversion ratio 100%, the gamma-butyrolacton selectivity is greater than 98%, and catalyst used 2000 hours continuously, active not obviously reduction.
Embodiment 4:
1. Preparation of catalysts
1.1. preparation Al
2O
3-TiO
2-active carbon blend
1.1.1.Al
2O
3-TiO
2The preparation of-active carbon blend
With 10.29gTiCl
4(6mL) hydrochloric acid with 1.0125mol/L is diluted to 1000mL, adds 45.65g Al (NO
3)
39H
2Pretreated 100～200 purpose active carbons of O and 4.15g, 70 ℃ were stirred 1 hour down; Under 70 ℃, slowly add the Na of 0.5mol/L then
2CO
3The aqueous solution mixes, and is that 6 depositions finish up to the pH value; Deposition ageing 12 hours is filtered, washing, 130 ℃ dry 12 hours down, grind to form 100～200 purpose powder, 500 ℃ of following roastings 3 hours make Al
2O
3-TiO
2-active carbon blend 20.62g.Wherein active carbon carries out preliminary treatment through following method: with 100～200 purpose active carbons, place the deionized water beaker is housed, stir heating down, seethed with excitement 2 hours, the cooled and filtered drying obtains.
1.1.2.Al
2O
3-TiO
2The composition analysis of-active carbon blend
Adopt XPS analysis Al
2O
3-TiO
2-active carbon blends surface atom valence state, and with the method for ICP-AES to Al
2O
3-TiO
2Each component of-active carbon blend is carried out the branch detection by quantitative, and analytical method is following:
Adopting the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, is excitaton source with Al K α, and the resolution ratio of instrument is 1.15eV, is fixed in behind the sample compressing tablet in the sample holder and tests.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company that each constituent content is analyzed.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, secondary air amount 1.0L/min, atomization gas flow 0.8L/min.
Analysis result shows Al
2O
3-TiO
2-active carbon blend consists of Al
2O
359w%, TiO
221w%, carbon 20w%.
1.2. preparation catalyst
1.2.1. Preparation of catalysts
With 24.15g CuNO
33H
2O and 15.12gZn (NO
3)
26H
2O is dissolved in the 1000mL deionized water, adds the Al that 8.31g step 1.1. obtains
2O
3-TiO
2-active carbon blend, 70 ℃ were stirred 1 hour down; Under 60 ℃, slowly add the Na of 0.5mol/L then
2CO
3The aqueous solution mixes, and is that 6 depositions finish up to the pH of system value; Precipitated ageing again 12 hours, and filtered, washing, 120 ℃ dry 12 hours down, 450 ℃ of following roastings 3 hours obtain catalyst finished product 20.54g.
1.2.2. the composition of catalyst
Adopt XPS analysis catalyst surface atom valence state, and with the method for ICP-AES each component of catalyst is carried out the branch quantitative analysis, analytical method is following:
Adopting the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, is excitaton source with Al K α, and the resolution ratio of instrument is 1.15eV, is fixed in behind the sample compressing tablet in the sample holder and tests.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company that each constituent content is analyzed.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, secondary air amount 1.0L/min, atomization gas flow 0.8L/min.
The result shows that this catalyst comprises the ZnO of the CuO of 39w%, 20w%, the Al of 24.2w%
2O
3, 8.6w% TiO
2, 8.2w% carbon.
Catalyst consists of the CuO of 39w%, the ZnO of 20w% and the Al of 41w%
2O
3-TiO
2-active carbon blend, wherein Al
2O
3-TiO
2-active carbon blend consists of Al
2O
359w%, TiO
221w%, carbon 20w%.
2. cis-butenedioic anhydride catalytic hydrogenation reaction
2.1 the catalyst granules that obtains in the step 1 is inserted in the fixed bed reactors of Φ 14mm, packed height is 5cm.H with 10%
2/ N
2Mist carries out activation to catalyst under 0.2MPa, 280 ℃, till the reactor outlet end does not have the globule.
2.2 at 270 ℃, under the normal pressure, cis-butenedioic anhydride liquid air speed 0.15h
-1, under 50: 1 the condition of hydrogen acid anhydride mol ratio catalyst is estimated.Adopt gas chromatographic analysis, cis-butenedioic anhydride conversion ratio 100%, the gamma-butyrolacton selectivity is greater than 98%, and catalyst used 2000 hours continuously, active not obviously reduction.
Embodiment 5:
1. Preparation of catalysts
1.1. preparation Al
2O
3-TiO
2-active carbon blend
1.1.1.Al
2O
3-TiO
2The preparation of-active carbon blend
With 10.04gTiCl
4(5.9mL) hydrochloric acid with 1.0125mol/L is diluted to 1000mL, adds 30.65g Al (NO
3)
39H
2Pretreated 100～200 purpose active carbons of O and 8.13g, 70 ℃ were stirred 1 hour down; Under 70 ℃, slowly add the Na of 0.5mol/L then
2CO
3The aqueous solution mixes, and is that 8 depositions finish up to the pH value; Deposition ageing 12 hours is filtered, washing, 130 ℃ dry 12 hours down, grind to form 100～200 purpose powder, 500 ℃ of following roastings 3 hours make Al
2O
3-TiO
2-active carbon blend 19.88g.Wherein active carbon carries out preliminary treatment through following method: with 100～200 purpose active carbons, place the deionized water beaker is housed, stir heating down, seethed with excitement 2 hours, the cooled and filtered drying obtains.
1.1.2.Al
2O
3-TiO
2The composition of-active carbon blend
Adopt XPS analysis Al
2O
3-TiO
2-active carbon blends surface atom valence state, and with the method for ICP-AES to Al
2O
3-TiO
2Each component of-active carbon blend is carried out the branch detection by quantitative, and analytical method is following:
Adopting the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, is excitaton source with Al K α, and the resolution ratio of instrument is 1.15eV, is fixed in behind the sample compressing tablet in the sample holder and tests.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company that each constituent content is analyzed.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, secondary air amount 1.0L/min, atomization gas flow 0.8L/min.
Analysis result shows Al
2O
3-TiO
2-active carbon blend consists of Al
2O
340.5w%, TiO
220.5w%, active carbon 39w%.
1.2. preparation catalyst
1.2.1. Preparation of catalysts
With 15.36g CuNO
33H
2O and 19.89gZn (NO
3)
26H
2O is dissolved in the 1000mL deionized water, adds the Al that 10.25g step 1.1. obtains
2O
3-TiO
2-active carbon blend, 70 ℃ were stirred 1 hour down; Under 70 ℃, slowly add the Na of 0.5mol/L then
2CO
3The aqueous solution mixes, and is that 7 depositions finish up to the pH of system value; Precipitated ageing again 12 hours, and filtered, washing, 120 ℃ dry 12 hours down, 450 ℃ of following roastings 3 hours obtain catalyst finished product 20.31g.
1.2.2. the composition of catalyst
Adopt XPS analysis catalyst surface atom valence state, and with the method for ICP-AES each component of catalyst is carried out the branch quantitative analysis, analytical method is following:
Adopting the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, is excitaton source with Al K α, and the resolution ratio of instrument is 1.15eV, is fixed in behind the sample compressing tablet in the sample holder and tests.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company that each constituent content is analyzed.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, secondary air amount 1.0L/min, atomization gas flow 0.8L/min.
The result shows that this catalyst comprises the ZnO of the CuO of 24w%, 26w%, the Al of 20.3w%
2O
3, 10.2w% TiO
2, 19.5w% carbon.
Catalyst consists of the CuO of 24w%, the ZnO of 26w% and the Al of 50w%
2O
3-TiO
2-active carbon blend, wherein Al
2O
3-TiO
2-active carbon blend consists of Al
2O
340.5w%, TiO
220.5w%, charcoal 39w%.
2. cis-butenedioic anhydride catalytic hydrogenation reaction
2.1 the catalyst granules that obtains in the step 1 is inserted in the fixed bed reactors of Φ 14mm, packed height is 5cm.H with 10%
2/ N
2Mist carries out activation to catalyst under 0.2MPa, 280 ℃, till the reactor outlet end does not have the globule.
2.2 at 270 ℃, under the normal pressure, cis-butenedioic anhydride liquid air speed 0.15h
-1, under 50: 1 the condition of hydrogen acid anhydride mol ratio catalyst is estimated.Adopt gas chromatographic analysis, cis-butenedioic anhydride conversion ratio 100%, the gamma-butyrolacton selectivity is greater than 98%, and catalyst used 2000 hours continuously, active not obviously reduction.
Embodiment 6:
1. Preparation of catalysts
1.1. preparation Al
2O
3-TiO
2-active carbon blend
1.1.1.Al
2O
3-TiO
2The preparation of-active carbon blend
With 24.00gTiCl
4(14.00mL) hydrochloric acid with 1.0125mol/L is diluted to 1000mL, adds 30.65g Al (NO
3)
39H
2Pretreated 100～200 purpose active carbons of O and 2.35g, 70 ℃ were stirred 1 hour down; Under 70 ℃, slowly add the Na of 0.5mol/L again
2CO
3The aqueous solution mixes, and is that 6.5 depositions finish up to the pH value; Precipitated ageing again 12 hours, and filtered, washing, 130 ℃ dry 12 hours down, grind to form 100～200 purpose powder, 500 ℃ of following roastings 3 hours make Al
2O
3-TiO
2-active carbon blend 20.03g.
Wherein active carbon carries out preliminary treatment through following method: with 100～200 purpose active carbons, place the deionized water beaker is housed, stir heating down, seethed with excitement 2 hours, the cooled and filtered drying obtains.
1.1.2.Al
2O
3-TiO
2The composition of-active carbon blend
Adopt XPS analysis Al
2O
3-TiO
2-active carbon blends surface atom valence state, and with the method for ICP-AES to Al
2O
3-TiO
2Each component of-active carbon blend is carried out the branch detection by quantitative, and analytical method is following:
Adopting the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, is excitaton source with Al K α, and the resolution ratio of instrument is 1.15eV, is fixed in behind the sample compressing tablet in the sample holder and tests.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company that each constituent content is analyzed.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, secondary air amount 1.0L/min, atomization gas flow 0.8L/min.
Analysis result shows Al
2O
3-TiO
2-active carbon blend consists of Al
2O
339.3w%, TiO
249.7w%, carbon 11w%.
1.2. preparation catalyst
1.2.1. Preparation of catalysts
With 7.56g CuNO
33H
2O and 37.55gZn (NO
3)
26H
2O is dissolved in the 1000mL deionized water, adds the Al that 8.22g step 1.1. obtains
2O
3-TiO
2-active carbon blend, 70 ℃ were stirred 1 hour down.Under 75 ℃, slowly add the Na of 0.1mol/L then
2CO
3NaHCO with 0.2mol/L
3The aqueous solution mixes, and is that 7 depositions finish up to the pH of system value; Precipitated ageing again 12 hours, and filtered, washing, 120 ℃ dry 12 hours down, 450 ℃ of following roastings 3 hours obtain catalyst finished product 20.31g.
1.2.2. the composition of catalyst
Adopt XPS analysis catalyst surface atom valence state, and with the method for ICP-AES each component of catalyst is carried out the branch quantitative analysis, analytical method is following:
Adopting the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, is excitaton source with Al K α, and the resolution ratio of instrument is 1.15eV, is fixed in behind the sample compressing tablet in the sample holder and tests.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company that each constituent content is analyzed.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, secondary air amount 1.0L/min, atomization gas flow 0.8L/min.
The result shows that this catalyst comprises the ZnO of the CuO of 11.6w%, 49.3w%, the Al of 15.4w%
2O
3, 19.4w% TiO
2, 4.3w% carbon.
Catalyst consists of the CuO of 11.6w%, the ZnO of 49.3w% and 39.1% Al
2O
3-TiO
2-active carbon blend, wherein Al
2O
3-TiO
2-active carbon blend consists of Al
2O
339.3w%, TiO
249.7w%, carbon 11w%.
2. cis-butenedioic anhydride catalytic hydrogenation reaction
2.1 the catalyst granules that obtains in the step 1 is inserted in the fixed bed reactors of Φ 14mm, packed height is 5cm.H with 10%
2/ N
2Mist carries out activation to catalyst under 0.2MPa, 280 ℃, till the reactor outlet end does not have the globule.
2.2 at 270 ℃, under the normal pressure, cis-butenedioic anhydride liquid air speed 0.15h
-1, under 50: 1 the condition of hydrogen acid anhydride mol ratio catalyst is estimated.Adopt gas chromatographic analysis, cis-butenedioic anhydride conversion ratio 100%, the gamma-butyrolacton selectivity is greater than 98%, and catalyst used 1800 hours continuously, active not obviously reduction.
Embodiment 7:
1. Preparation of catalysts
1.1. preparation Al
2O
3-TiO
2-active carbon blend
1.1.1.Al
2O
3-TiO
2The preparation of-active carbon blend
With 21.24gTiCl
4(12.40mL) hydrochloric acid with 1.0125mol/L is diluted to 1000mL, adds 16.50g Al (NO
3)
39H
2Pretreated 100～200 purpose active carbons of O and 7.52g, 70 ℃ were stirred 1 hour down; Under 70 ℃, slowly add the Na of 0.5mol/L then
2CO
3The aqueous solution mixes, and is that 7.5 depositions finish up to the pH value; Precipitated ageing again 12 hours, and filtered, washing, 130 ℃ dry 12 hours down, grind to form 100～200 purpose powder, 500 ℃ of following roastings 3 hours make Al
2O
3-TiO
2-active carbon blend 20.53g.
Wherein active carbon carries out preliminary treatment through following method: with 100～200 purpose active carbons, place the deionized water beaker is housed, stir heating down, seethed with excitement 2 hours, the cooled and filtered drying obtains.
1.1.2.Al
2O
3-TiO
2The composition of-active carbon blend
Adopt XPS analysis Al
2O
3-TiO
2-active carbon blends surface atom valence state, and with the method for ICP-AES to Al
2O
3-TiO
2Each component of-active carbon blend is carried out the branch detection by quantitative, and analytical method is following:
Adopting the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, is excitaton source with Al K α, and the resolution ratio of instrument is 1.15eV, is fixed in behind the sample compressing tablet in the sample holder and tests.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company that each constituent content is analyzed.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, secondary air amount 1.0L/min, atomization gas flow 0.8L/min.
Analysis result shows Al
2O
3-TiO
2-active carbon blend consists of Al
2O
321.4w%, TiO
242.6w%, carbon 36w%.
1.2. preparation catalyst
1.2.1. Preparation of catalysts
With 30.36g CuNO
33H
2O and 9.89gZn (NO
3)
26H
2O is dissolved in the 1000mL deionized water, adds the Al that 8.05g step 1.1. obtains
2O
3-TiO
2-active carbon blend, 70 ℃ were stirred 1 hour down; Under 80 ℃, slowly add the Na of 0.3mol/L then
2CO
3NH with 0.3mol/L
4HCO
3The aqueous solution mixes, and is that 7 depositions finish up to the pH of system value; Precipitated ageing again 12 hours, and filtered, washing, 120 ℃ dry 12 hours down, 450 ℃ of following roastings 3 hours obtain catalyst finished product 20.31g.
1.2.2. the composition of catalyst
Adopt XPS analysis catalyst surface atom valence state, and with the method for ICP-AES each component of catalyst is carried out the branch quantitative analysis, analytical method is following:
Adopting the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, is excitaton source with Al K α, and the resolution ratio of instrument is 1.15eV, is fixed in behind the sample compressing tablet in the sample holder and tests.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company that each constituent content is analyzed.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, secondary air amount 1.0L/min, atomization gas flow 0.8L/min.
The result shows that this catalyst comprises the ZnO of the CuO of 48.3w%, 12.7w%, the Al of 8.3w%
2O
3, 16.6w% TiO
2, 14.1w% carbon.
Catalyst consists of the CuO of 48.3w%, the ZnO of 12.7w% and the Al of 39w%
2O
3-TiO
2-active carbon blend, wherein Al
2O
3-TiO
2-active carbon blend consists of Al
2O
321.4w%, TiO
242.6w%, carbon 36w%.
2. cis-butenedioic anhydride catalytic hydrogenation reaction
2.1 the catalyst granules that obtains in the step 1 is inserted in the fixed bed reactors of Φ 14mm, packed height is 5cm.H with 10%
2/ N
2Mist carries out activation to catalyst under 0.2MPa, 280 ℃, till the reactor outlet end does not have the globule.
2.2 at 270 ℃, under the normal pressure, cis-butenedioic anhydride liquid air speed 0.15h
-1, under 50: 1 the condition of hydrogen acid anhydride mol ratio catalyst is estimated.Adopt gas chromatographic analysis, cis-butenedioic anhydride conversion ratio 100%, the gamma-butyrolacton selectivity is greater than 98%, and catalyst used 1800 hours continuously, active not obviously reduction.
Embodiment 8:
1. Preparation of catalysts
1.1. preparation Al
2O
3-TiO
2-active carbon blend
1.1.1.Al
2O
3-TiO
2The preparation of-active carbon blend
With 5.05gTiCl
4(3.00mL) hydrochloric acid with 1.0125mol/L is diluted to 1000mL, adds 60.65g Al (NO
3)
39H
2Pretreated 100～200 purpose active carbons of O and 2.5g, 70 ℃ were stirred 1 hour down; Under 70 ℃, slowly add the Na of 0.5mol/L then
2CO
3The aqueous solution mixes, and is that 7.0 depositions finish up to the pH value; Deposition ageing 12 hours is filtered, washing, 130 ℃ dry 12 hours down, grind to form 100～200 purpose powder, 500 ℃ of following roastings 3 hours make Al
2O
3-TiO
2-active carbon blend 19.58g.Wherein active carbon carries out preliminary treatment through following method: with 100～200 purpose active carbons, place the deionized water beaker is housed, stir heating down, seethed with excitement 2 hours, the cooled and filtered drying obtains.
1.1.2.Al
2O
3-TiO
2The composition of-active carbon blend
Adopt XPS analysis Al
2O
3-TiO
2-active carbon blends surface atom valence state, and with the method for ICP-AES to Al
2O
3-TiO
2Each component of-active carbon blend is carried out the branch detection by quantitative, and analytical method is following:
Adopting the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, is excitaton source with Al K α, and the resolution ratio of instrument is 1.15eV, is fixed in behind the sample compressing tablet in the sample holder and tests.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company that each constituent content is analyzed.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, secondary air amount 1.0L/min, atomization gas flow 0.8L/min.
Analysis result shows Al
2O
3-TiO
2-active carbon blend consists of Al
2O
379.2w%, TiO
210.1w%, carbon 10.7w%.
1.2. preparation catalyst
1.2.1. Preparation of catalysts
With 28.52g CuNO
33H
2O and 24.15gZn (NO
3)
26H
2O is dissolved in the 1000mL deionized water, adds the Al that 4.58g step 1.1. obtains
2O
3-TiO
2-active carbon blend, 70 ℃ were stirred 1 hour down; Under 65 ℃, slowly add the Na of 0.2mol/L then
2CO
3, the NaOH of 0.2mol/L, the KHCO of 0.1mol/L
3, 0.1mol/L the KOH aqueous solution, mix, be that 7 depositions finish up to the pH of system value; Precipitated ageing again 12 hours, and filtered, washing, 120 ℃ dry 12 hours down, 450 ℃ of following roastings 3 hours obtain catalyst finished product 20.31g.
1.2.2. the composition of catalyst
Adopt XPS analysis catalyst surface atom valence state, and with the method for ICP-AES each component of catalyst is carried out the branch quantitative analysis, analytical method is following:
Adopting the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, is excitaton source with Al K α, and the resolution ratio of instrument is 1.15eV, is fixed in behind the sample compressing tablet in the sample holder and tests.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company that each constituent content is analyzed.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, secondary air amount 1.0L/min, atomization gas flow 0.8L/min.
The result shows that this catalyst comprises the ZnO of the CuO of 45.5w%, 32w%, the Al of 17.8w%
2O
3, 2.3w% TiO
2, 2.4w% carbon.
Catalyst consists of the CuO of 45.5w%, the ZnO of 32w% and the Al of 22.5w%
2O
3-TiO
2-active carbon blend, wherein Al
2O
3-TiO
2The active carbon blend consists of Al
2O
379.2w%, TiO
210.1w%, carbon 10.7w%.
2. cis-butenedioic anhydride catalytic hydrogenation reaction
2.1 the catalyst granules that obtains in the step 1 is inserted in the fixed bed reactors of Φ 14mm, packed height is 5cm.H with 10%
2/ N
2Mist carries out activation to catalyst under 0.2MPa, 280 ℃, till the reactor outlet end does not have the globule.
2.2 at 270 ℃, under the normal pressure, cis-butenedioic anhydride liquid air speed 0.15h
-1, under 50: 1 the condition of hydrogen acid anhydride mol ratio catalyst is estimated.Adopt gas chromatographic analysis, cis-butenedioic anhydride conversion ratio 100%, the gamma-butyrolacton selectivity is greater than 98%, and catalyst used 1900 hours continuously, active not obviously reduction.
Embodiment 9:
1. Preparation of catalysts
1.1. preparation Al
2O
3-TiO
2-active carbon blend
1.1.1.Al
2O
3-TiO
2The preparation of-active carbon blend
With 6.25gTiCl
4(3.70mL) hydrochloric acid with 1.0125mol/L is diluted to 1000mL, adds 29.55g Al (NO
3)
39H
2100～200 purpose active carbons of O and 10.05g, 70 ℃ were stirred 1 hour down; Under 70 ℃, slowly add the Na of 0.5mol/L then
2CO
3The aqueous solution mixes, and is that 7.4 depositions finish up to the pH value; Precipitated ageing again 12 hours, and filtered, washing, 130 ℃ dry 12 hours down, grind to form 100～200 purpose powder, 500 ℃ of following roastings 3 hours make Al
2O
3-TiO
2-active carbon blend 19.79g.
1.1.2.Al
2O
3-TiO
2The composition of-active carbon blend
Adopt XPS analysis Al
2O
3-TiO
2-active carbon blends surface atom valence state, and with the method for ICP-AES to Al
2O
3-TiO
2Each component of-active carbon blend is carried out the branch detection by quantitative, and analytical method is following:
Adopting the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, is excitaton source with Al K α, and the resolution ratio of instrument is 1.15eV, is fixed in behind the sample compressing tablet in the sample holder and tests.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company that each constituent content is analyzed.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, secondary air amount 1.0L/min, atomization gas flow 0.8L/min.
Analysis result shows Al
2O
3-TiO
2-active carbon blend consists of Al
2O
338.5w%, TiO
213.2w%, carbon 48.3w%.
1.2. preparation catalyst
1.2.1. Preparation of catalysts
With 6.55g CuNO
33H
2O and 8.25gZn (NO
3)
26H
2O is dissolved in the 1000mL deionized water, adds the Al that 15.75g step 1.1. obtains
2O
3-TiO
2-active carbon blend, 70 ℃ were stirred 1 hour down; Under 60 ℃, slowly add the Na of 0.2mol/L then
2CO
3, 0.3mol/L NaHCO
3K with 0.5mol/L
2CO
3The aqueous solution mixes, and is that 7 depositions finish up to the pH of system value; Precipitated ageing again 12 hours, and filtered, washing, 120 ℃ dry 12 hours down, 450 ℃ of following roastings 3 hours obtain catalyst finished product 20.31g.
1.2.2. the composition of catalyst
Adopt XPS analysis catalyst surface atom valence state, and with the method for ICP-AES each component of catalyst is carried out the branch quantitative analysis, analytical method is following:
Adopting the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, is excitaton source with Al K α, and the resolution ratio of instrument is 1.15eV, is fixed in behind the sample compressing tablet in the sample holder and detects.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company that each constituent content is analyzed.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, secondary air amount 1.0L/min, atomization gas flow 0.8L/min.
The result shows that this catalyst comprises the ZnO of the CuO of 10.5w%, 10.9w%, the Al of 30.3w%
2O
3, 10.4w% TiO
2, 37.9w% carbon.
Catalyst consists of the CuO of 10.5w%, the ZnO of 10.9w% and the Al of 78.6w%
2O
3-TiO
2-active carbon blend, wherein Al
2O
3-TiO
2-active carbon blend consists of Al
2O
338.5w%, TiO
213.2w%, carbon 48.3w%.
2. cis-butenedioic anhydride catalytic hydrogenation reaction
2.1 the catalyst granules that obtains in the step 1 is inserted in the fixed bed reactors of Φ 14mm, packed height is 5cm.H2/N2 mist with 10% carries out activation to catalyst under 0.2MPa, 280 ℃, till the reactor outlet end does not have the globule.
2.2 at 270 ℃, under the normal pressure, cis-butenedioic anhydride liquid air speed 0.15h-1 estimates catalyst under 50: 1 the condition of hydrogen acid anhydride mol ratio.Adopt gas chromatographic analysis, cis-butenedioic anhydride conversion ratio 100%, the gamma-butyrolacton selectivity is greater than 98%, and catalyst used 1800 hours continuously, active not obviously reduction.
Claims (4)
1. a cis-anhydride normal pressure gas phase hydrogenation prepares the catalyst that gamma-butyrolacton is used, and this catalyst is by 10 ~ 49w%CuO, 10 ~ 50w%ZnO and 22 ~ 79w%Al
2O
3-TiO
2-active carbon blend is formed, wherein Al
2O
3-TiO
2-active carbon blend is by 21 ~ 80w%Al
2O
3, 10 ~ 50w%TiO
2Form with 10 ~ 49w% active carbon, and prepare by following method:
(1) with Cu (NO
3)
23H
2O and Zn (NO
3)
29H
2O is dissolved in the deionized water, adds Al
2O
3-TiO
2-active carbon blend, 70 ℃ were stirred 1 hour down, wherein Cu (NO
3)
23H
2O, Zn (NO
3)
29H
2O and Al
2O
3-TiO
2The weight ratio of-active carbon blend is Cu (NO
3)
23H
2O:Zn (NO
3)
29H
2O:Al
2O
3-TiO
2-active carbon blend=13 ~ 61:16 ~ 76:9 ~ 32;
(2) under 60 ~ 80 ℃, slowly add the precipitating reagent aqueous solution of 0.1 ~ 1mol/L, mix, be that 6 ~ 8 depositions finish up to the pH of system value, wherein said precipitating reagent is Na
2CO
3, NaHCO
3, NaOH, K
2CO
3, KHCO
3, KOH, NH
4HCO
3In one or more;
(3) the deposition ageing is 12 hours, filters, washs; 120 ℃ dry 12 hours down, 450 ℃ of following roastings 3 hours obtain described catalyst;
Wherein, described Al
2O
3-TiO
2-active carbon blend is prepared by following method:
With TiCl
4With the watery hydrochloric acid dilution, add Al (NO
3)
39H
2O and 100 ~ 200 purpose active carbon powders, 70 ℃ were stirred 1 hour down, wherein TiCl
4, Al (NO
3)
39H
2O and 100 ~ 200 purpose active carbon weight ratios are TiCl
4: Al (NO
3)
39H
2O:100 ~ 200 purpose active carbon=10.1 ~ 42.5:33～121.3:4.7 ~ 20.1; Under 70 ℃, slowly add the Na of 0.5mol/L
2CO
3The aqueous solution mixes, and is that 6 ~ 8 depositions finish up to the pH of system value; Deposition ageing 12 hours is filtered, is washed, and drying is 12 hours under 130 ℃, grinds to form 100 ~ 200 purpose powder, 500 ℃ of following calcinations 3 hours, obtains described Al
2O
3-TiO
2-active carbon blend.
2. the described cis-anhydride normal pressure gas phase hydrogenation of claim 1 prepares the catalyst that gamma-butyrolacton is used, and it is characterized in that, described catalyst is by 20 ~ 45w%CuO, 20 ~ 40w%ZnO and 40 ~ 60w%Al
2O
3-TiO
2-active carbon blend is formed, but does not comprise CuO, ZnO and Al
2O
3-TiO
2The content sum of-active carbon blend is greater than 100% catalyst.
3. the described cis-anhydride normal pressure gas phase hydrogenation of claim 1 prepares the catalyst that gamma-butyrolacton is used, and it is characterized in that, described precipitating reagent is Na
2CO
3
4. one of them described cis-anhydride normal pressure gas phase hydrogenation of claim 1 to 3 prepares the catalyst that gamma-butyrolacton is used, and it is characterized in that described Al
2O
3-TiO
2-active carbon blend best group becomes the Al of 40 ~ 60w%
2O
3, 20 ~ 40w% TiO
2Active carbon with 20 ~ 40w%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110133604A CN102247853B (en) | 2011-05-23 | 2011-05-23 | Catalyst for preparing gamma-butyrolactone through maleic anhydride normal-pressure gas-phase hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110133604A CN102247853B (en) | 2011-05-23 | 2011-05-23 | Catalyst for preparing gamma-butyrolactone through maleic anhydride normal-pressure gas-phase hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102247853A CN102247853A (en) | 2011-11-23 |
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| CN1890231A (en) * | 2003-12-09 | 2007-01-03 | 巴斯福股份公司 | Method for the production of defined mixtures of THF BDO and GBL by gas phase hydrogenation |
| CN101591222A (en) * | 2009-04-23 | 2009-12-02 | 上海华谊丙烯酸有限公司 | A kind of method of hydrogenating glucose to prepare sorbierite |
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| JP2001261305A (en) * | 2000-03-21 | 2001-09-26 | Toyota Motor Corp | Apparatus for reforming fuel |
| JP2005211808A (en) * | 2004-01-30 | 2005-08-11 | Mitsubishi Heavy Ind Ltd | Catalyst for reforming dimethyl ether |
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| CN1890231A (en) * | 2003-12-09 | 2007-01-03 | 巴斯福股份公司 | Method for the production of defined mixtures of THF BDO and GBL by gas phase hydrogenation |
| CN101591222A (en) * | 2009-04-23 | 2009-12-02 | 上海华谊丙烯酸有限公司 | A kind of method of hydrogenating glucose to prepare sorbierite |
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| JP特开2001-261305A 2001.09.26 |
| JP特开2005-211808A 2005.08.11 |
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